Phenyl-azo-aniline dyes

ABSTRACT

Azo compounds having the formula ##SPC1## 
     In which X and Y are hydrogen or a substituent, R 1  is alkyl or R 4  , R 2  is hydrogen, alkyl or alkoxy, R 3  is hydrogen or alkyl, and R 4  is aryl, cyclohexyl, alkoxy, benzyl, 2-furyl or --R 5  --O--Z in which R 5  is alkylene and Z is aryl. The compounds are useful for dyeing polyester fibers and exhibit good dyeability, fastness to light and resistance to sublimation.

This is a continuation-in-part application of U.S. patent application Ser. No. 194,000 filed Oct. 29, 1971, now abandoned.

This invention concerns certain novel azo compounds useful for dyeing polyester textile materials. Our novel azo compounds have the formula ##SPC2##

Wherein

D is a group having the formula ##SPC3## ##SPC4##

In which

X is hydrogen, chlorine, bromine, cyano, lower alkylsulfonyl, or nitro; and

Y is hydrogen or cyano;

R¹ is lower alkyl; lower alkyl substituted with halogen, hydroxy, lower alkoxy, lower alkanoyloxy, cyano or carbamoyl; or a group represented by R⁴ ;

R² is hydrogen, lower alkyl or lower alkoxy;

R³ is hydrogen or alkyl of up to about eight carbon atoms; and

R⁴ is aryl, cyclohexyl, lower alkoxy, benzyl, 2-furyl or the group --R⁵ --O--Z in which R⁵ is alkylene of up to about six carbon atoms and Z is aryl;

In which

Each aryl group is phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.

Our novel compounds, in general, exhibit a desirable combination of good properties when applied to polyester textile fibers according to conventional techniques. The compounds of the invention possess excellent fastness to light and resistance to sublimation. Our compounds also exhibit good dyeability and therefore produce on polyester fibers deep, level dyeings which do not crock. The improved dyeability also is manifested by the good build-up which our compounds exhibit. This combination of properties renders our compounds valuable polyester dyes and distinguishes them from the compounds disclosed in Belgian Pat. No. 654,637 and Canadian Pat. No. 754,146.

The substituents represented by each of R¹, R², R³, R⁴, R⁵, X and Y are well known in the art and/or can be derived from available chemicals according to known means. As used herein to describe an alkyl moiety, "lower" designates a a carbon content of from about one to about four carbon atoms. Chlorine and bromine are preferred halogen atoms.

A group of our novel compounds which are particularly valuable polyester dyes because of the cost:performance ratio of each member thereof corresponds to Formula (I) wherein

X is hydrogen, chlorine, bromine, cyano, lower alkylsulfonyl or nitro;

Y is hydrogen or cyano;

R¹ is lower alkyl or lower alkoxy;

R² is hydrogen;

R³ is lower alkyl; and

R⁴ is phenyl, lower alkylphenyl, lower alkoxyphenyl, chlorophenyl, bromophenyl, cyclohexyl, benzyl, 2-furyl or the group --CH₂ O--Z in which Z is phenyl, lower alkylphenyl or lower alkoxyphenyl.

The novel compounds of our invention are prepared by diazotizing an amine having the formula

    D--NH.sub.2                                                (II)

and coupling the resulting diazonium salt with a coupler having the formula ##SPC5##

according to conventional procedures. Our azo compounds which contain a cyano-substituted phenyl diazo component also can be obtained by reacting the analogous halo-substituted azo compound with a cyanide salt in the presence of a copper catalyst.

The amines of Formula (II) are known compounds and/or can be obtained by known chemical techniques. The couplers of Formula (II) are prepared by cyanomethylating an m-acylamidoaniline compound, reducing the N-cyanomethyl-m-acylamidoaniline to the N-aminoethyl compound and then acylating the N-aminoethyl compound with a known acylating agent. The acylating step can be performed at elevated temperatures, e.g., 95°-100°C., in the presence of a solvent such as pyridine. The following couplers are prepared by treating N-(2-aminoethyl)-N-ethyl-m-acetamidoaniline with the acylating agents listed below:

    __________________________________________________________________________                                  Melting                                                                        Point,                                            Acylating Agent Coupler      °C.                                        __________________________________________________________________________     Benzoyl chloride                                                                          N-(2-benzaimdoethyl)-N-ethyl-m-                                                                   98-100                                                      acetamidoaniline                                                    2-Furoyl chloride                                                                         N-(2-[2-furoyl]aminoethyl)-N-                                                                    149-150                                                      ethyl-m-acetamidoaniline                                            Cyclohexoyl                                                                               N-(2-cyclohexoylaminoethyl)-N-                                                                   89-91                                             chloride   ethyl-m-acetamidoaniline                                            Phenylacetyl                                                                              N-(2-phenylacetamidoethyl)-N-                                                                    153-155                                           chloride   ethyl-m-acetamidoaniline                                            p-Methoxybenzoyl                                                                          N-(2-p-methoxybenzamidoethyl)-                                                                   174-176                                           chloride   N-ethyl-m-acetamidoaniline                                          Phenoxyacetyl                                                                             N-(2-phenoxyacetamidoethyl)-N-                                                                   103-106                                           chloride   ethyl-m-acetamidoaniline                                            Ethyl Chloro-                                                                             N-(2-ethoxycarbonylaminoethyl)-                                                                  120-122                                           formate    N-ethyl-m-acetamidoaniline                                          __________________________________________________________________________

The preparation and use of our novel compounds is further illustrated by the following examples.

EXAMPLE 1

p-Nitroaniline (6.9 g.) is dissolved in 5.4 ml. of conc. H₂ SO₄ and 12.6 ml. of water. This solution is poured onto 50 g. of crushed ice. To this is added a solution of 3.6 g. of NaNO₂ in 8 ml. of water. The diazotization reaction mixture is stirred for 15 minutes. An aliquot of this diazonium solution (0.005 mole) is added to 0.005 mole of the coupler m-acetamido-N-ethyl-N,2-(phenoxyacetamido)ethylaniline which is dissolved in 25 ml. of 1:5 acid (1 part propionic:5 parts acetic acid), with cooling to keep the temperature below 15°C. The coupling mixture is buffered by adding ammonium acetate and allowed to stand for one hour. The reaction mixture is drowned with water and the product is collected by filtration and dried in air. The product is slurried in hot methanol, cooled, collected by filtration and washed with methanol to yield 1.5 g. of the compound having the formula ##SPC6##

This compound has a visible absorption maximum at 506 nm. (acetone) and produces bright red shades on polyester fibers. The light-fastness, resistance to sublimation and build-up properties of this compound are excellent on polyester fibers.

EXAMPLE 2

2-Amino-5-nitrothiazole (1.45 g.) is dissolved in 25 g. of 50% H₂ SO₄. The solution is cooled to -15°C. and a solution of 0.76 g. of NaNO₂ in 5 ml. of conc. H₂ SO₄ is added below -10°C. The reaction mixture is stirred for 15 minutes at -15°C. and then added to a chilled solution of N-ethyl-N-[2-(4-methoxybenzamido)ethyl]-m-acetamidoaniline in 50 ml. of 50% H₂ SO₄ plus 20 ml. of 1:5 acid. The coupling is allowed to stand for 15 minutes and is then drowned with water. The product is collected by filtration, washed with water and dried in air and then is purified by reslurrying in methanol. The visible absorption maximum of this compound is 585 nm. (acetone). This azo compound produces bright blue shades on polyester fibers, has good light-fastness, resistance to sublimation and build-up and has the structure ##SPC7##

The azo compounds set forth in Table I are prepared by the procedures described in the preceding examples and conform to Formula (I). The color given for each compound designates the shade it produces on polyester fibers.

                                      TABLE I                                      __________________________________________________________________________     Ex.                                                                            No.     D            R.sup.1 R.sup.2                                                                              R.sup.3       R.sup.4  Color                __________________________________________________________________________      3 2-Br-6-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                     H                                                 C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                           Reddish-                                                                       Blue                  4 2,6-di-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                         5 4-NO.sub.2 -phenyl                                                          CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Red                                                                          6 2-Cl-4-NO.sub.2 -phenyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                CH.sub.2 C.sub.6 H.sub.5                                                          Red                                                                          7 2-Cl-4-NO.sub.2 -phenyl                                                     C.sub.2 H.sub.5                                                                   H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Red                                                                          8 2-Cl-4-NO.sub.2 -phenyl                                                     OC.sub.2 H.sub.5                                                                  H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Red                                                                          9 2-Cl-4-NO.sub.2 -phenyl                                                     CH.sub.2 Cl                                                                    CH.sub.3                                                                          H                                                                           C.sub.6 H.sub.5                                                                   Red                                                                         10 2-Cl-4-NO.sub.2 -phenyl                                                     CH.sub.2 OCH.sub.3                                                                H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Red                                                                         11 2-Br-4-NO.sub.2 -phenyl                                                     CH.sub.2 OH                                                                       H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub. 5                                                                  Red                                                                         12 2-CN-4-NO.sub.2 -phenyl                                                     CH.sub.2 OOCCH.sub.3                                                              H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Violet                                                                      13 2-CN-4-NO.sub.2 -phenyl                                                     C.sub.6 H.sub.5                                                                   H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Violet                                                                      14 2-CN-4-NO.sub.2 -phenyl                                                     CH.sub.2 C.sub.6 H.sub.5                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Violet                                                                      15 2-CN-4-NO.sub.2 -phenyl                                                     CH.sub.2 OC.sub.6 H.sub.5                                                         H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Violet                                                                      16 2-CN-4-NO.sub.2 -phenyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Violet                                                                      17 2-Cl-6-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        18 2-Br-6-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                     C.sub.6 H.sub.5                                                                   Blue                                                                        19 2-Br-6-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                    C.sub.6 H.sub.5                                                                   Blue                                                                        20 2-Br-6-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           CH(CH.sub.3)C.sub.2 H.sub.5                                                    C.sub.6 H.sub.5                                                                   Blue                                                                        21 2-Br-6-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.11                                                                  Blue                                                                        22 2-Br-6-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                CH.sub.2 OC.sub.6 H.sub.5                                                         Blue                                                                        23 2,6-di-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        24 2,6-di-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                CH=CHCH=CHO                                                                       Blue                                                                        25 2,6-di-CN-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.4 -p-OCH.sub.3                                                      Blue                                                                        26 2-CN-6-CH.sub.3 SO.sub.2 -4-NO.sub.2 -phenyl                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        27 2-CN-4,6-di-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        28 2-CN-4,6-di-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.4 -p-OCH.sub.3                                                      Blue                                                                        29 2-CN-4,6-di-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.4 -p-Cl                                                             Blue                                                                        30 2-CN-4,6-di-NO.sub.2 -phenyl                                                CH.sub.3                                                                       OCH.sub.3                                                                      C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Blue                                                                        31 2-CN-4-NO.sub.2 -6-CF.sub.3 -phenyl                                         CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        32 2-CN-4-NO.sub.2 6-(CH.sub.3).sub.2 NSO.sub.2 -                              CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                           phenyl                                                                      33 2-CN-4-NO.sub.2 -6-COCH.sub.3 -phenyl                                       CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        34 2-CN-4-NO.sub.2 -6-COOC.sub.2 H.sub. 5 -phenyl                              CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        35 2,6-di-Br-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Red                                                                         36 2-Br-6-Cl-4-NO.sub.2 -phenyl                                                CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Red                                                                         37 2-CN-6-CH.sub.2 SO.sub.2 -4-NO.sub.2 -phenyl                                C.sub.6 H.sub.11                                                                  H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Violet                                                                      38 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        39 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.11                                                                  Blue                                                                        40 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Blue                                                                        41 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                CH.sub.2 C.sub.6 H.sub.5                                                          Blue                                                                        42 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.4 -p-Cl                                                             Blue                                                                        43 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.4 -p-CH.sub.3                                                       Blue                                                                        44 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.4 -o-Cl                                                             Blue                                                                        45 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.4 -p-C(CH.sub.3).sub. 3                                             Blue                                                                        46 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.3                                                                          H                                                                           C.sub.2 H.sub.5                                                                C=CHCH=CHO                                                                        Blue                                                                        47 5-NO.sub.2 -2-thiazolyl                                                     C.sub.2 H.sub.5                                                                   H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        48 5-NO.sub.2 -2-thiazolyl                                                     C.sub.2 H.sub.5                                                                   H                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                     C.sub.6 H.sub.5                                                                   Blue                                                                        49 5-NO.sub.2 -2-thiazolyl                                                     C.sub.2 H.sub.5                                                                   H                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                    C.sub.6 H.sub.5                                                                   Blue                                                                        50 5-NO.sub.2 -2-thiazolyl                                                     C.sub.2 H.sub.5                                                                CH.sub.3                                                                          H                                                                           C.sub.6 H.sub.5                                                                   Blue                                                                        51 5-NO.sub.2 -2-thiazolyl                                                     OC.sub.2 H.sub.5                                                                  H                                                                           (CH.sub.2).sub.3 CH.sub.3                                                      OC.sub.2 H.sub.5                                                                  Blue                                                                        52 5-NO.sub.2 -2-thiazolyl                                                     C.sub.6 H.sub.11                                                                  H                                                                           CH.sub.2 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 CH.sub.3                          CH.sub.2 OC.sub.6 H.sub.5                                                         Blue                                                                        53 5-NO.sub.2 -2-thiazolyl                                                     C.sub.6 H.sub.5                                                                   H                                                                           C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Blue                                                                        54 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.2 C.sub.6 H.sub.5                                                          H                                                                           C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Blue                                                                        55 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.2 OC.sub.6 H.sub.5                                                         H                                                                           C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Blue                                                                        56 5-NO.sub.2 -2-thiazolyl                                                     CH.sub.2 CH.sub.2 Cl                                                              H                                                                           C.sub.2 H.sub.5                                                                C.sub.6 H.sub.5                                                                   Blue                                                                        57 5-NO.sub.2 -2-thiazolyl                                                     C.sub.6 H.sub.4 -p-OCH.sub.3                                                      H                                                                           C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Blue                                                                        58 5-NO.sub.2 -2-thiazolyl                                                     C.sub.6 H.sub.4 -p-Cl                                                             H                                                                           C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                  Blue                                                                        __________________________________________________________________________

The preferred dyes have the formula ##SPC8##

wherein

X is hydrogen, chlorine, bromine, cyano, lower alkylsulfonyl, nitro;

Y is hydrogen or cyano;

R¹ is lower alkyl; lower alkyl substituted with halogen, hydroxy, lower alkoxy, lower alkanoyloxy, cyano or carbamoyl; or a group represented by R⁴ ;

R² is hydrogen, lower alkyl or lower alkoxy;

R³ is hydrogen or alkyl of up to about eight carbon atoms; and

R⁴ is aryl, cyclohexyl, lower alkoxy, benzyl, 2-furyl or the group --R⁵ --O--Z in which R⁵ is alkylene of up to about six carbon atoms and Z is aryl;

in which

each aryl group is phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.

It is particularly noted that the monohalogen (chlorine or bromine) substituted diazo component gives markedly superior light fastness over the dihalogen substitution.

The polyester textile materials dyeable with our novel compounds and the techniques by which our compounds are applied thereto are well known in the art. For example, the compounds can be applied to polyester fibers according to the procedures described in French Pat. No. 2,008,404.

This invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A compound having the formula ##SPC9##wherein X is hydrogen, chlorine, bromine, cyano, lower alkylsulfonyl, nitro; Y is hydrogen or cyano; R¹ is lower alkyl; lower alkyl substituted with chlorine, hydroxy, lower alkoxy, lower alkanoyloxy, cyano or carbamoyl; or a group represented by R⁴ ; R² is hydrogen, lower alkyl or lower alkoxy; R³ is hydrogen or alkyl of up to eight carbon atoms; and R⁴ is aryl, cyclohexyl, lower alkoxy, benzyl, or the group --R⁵ --O--Z in which R⁵ is alkylene of up to six carbon atoms and Z is aryl; in whicheach aryl group is phenyl or phenyl substituted with lower alkyl, lower alkoxy, chlorine, or bromine.
 2. A compound according to claim 1 having the formula ##SPC10##wherein X is hydrogen, chlorine, bromine, cyano, lower alkylsulfonyl or nitro; Y is hydrogen or cyano; R¹ is lower alkyl or lower alkoxy; R³ is lower alkyl; and R⁴ is phenyl, lower alkylphenyl, lower alkoxyphenyl, chlorophenyl, bromophenyl, cyclohexyl, benzyl, or the group --CH₂ O--Z in which Z is phenyl, lower alkylphenyl or lower alkoxyphenyl.
 3. A compound according to claim 1 having the formula ##SPC11##
 4. A compound according to claim 1 having the formula ##SPC12##
 5. A compound according to claim 1 having the formula ##SPC13##
 6. A compound according to claim 1 having the formula ##SPC14##
 7. A compound according to claim 1 having the formula ##SPC15##
 8. A compound according to claim 1 having the formula ##SPC16## 